Composition of matter and method of making same



Patented May 1945 2,375,530 COMPOSITION OF MATTER AND METHO OF MAKINGSAME Melvin De Groote, University City, Bernhard Keiser, Webster Groves,and Arthur F. Wirtel,

Kirkwood Mo.,

assignors to Petrolite Com ration, Ltd., Wilmington, Del., a corporationof Delaware No Drawing. Application June 21, 1943,

Serial No. 491,732

4 Claims. (Cl. 260-405) This invention relates to a new composition ofmatter, our present application being a continuation-in-part of ourpending application Serial No. 440,750, filed April 27, 1942, now PatentNo. 2,340,306.

One object of our invention is to provide a chemical product or compoundthat is particularly adapted fr. use as a demulsiiier in the resolutionof crude oil emulsions.

Another object of our invention is to provide a practicable method formanufacturing said new chemical product or compound.

Although one of the primary objects of our invention is to provide a newcompound or composition of matter that is an efficient demulsifler forcrude oil emulsions'of the water-in-oil type,

the said compound or composition of matter is adapted for use in otherarts, as hereinafter indicated. It also may have additional uses invarious other fields which have not yet been investigated.

The composition of matter herein described, particularly when it isintended to be used as a demulsifler for petroleum emulsions of thewaterin-oil type, is obtained by the hydroxy-acetylation of blown oroxidized ricinoleic acid compounds, or compounds of the kind hereinafterdescribed.

' It is well known that oxidized oils can be obtained from castor oil,ricinoleic acid and various derivatives of ricinoleic acid, such as:Monoricinolein, diricinolein and polyricinoleic acids.

. They are produced by the common practice of blowing or oxidizingcastor oil and similar fatty oils or acids, particularly non-dryingunsaturated fatty oils, by means of a gaseousmedium, such as air,oxygen, ozone, or ozonized air, The gaseous medium, such as air, may bemoist or dry, and

the oxididation may take place in the presence or absence of a catalyst.The catalyst may be of a metallic type, such as lead ricinoleate, cobaltricinoleate, manganese ricinoleate, etc.; or it may be of the organictype which produces a peroxide such as alpha-pinene, linseed oil, etc.Oxidation may take place at atmospheric pressure or superatmosphericpressure, i. e., pressures up to or in' cluding 200 pounds gaugepressure, and at any temperature slightly above the boiling point ofwater, for instance, 120 C., up to anytemperature which does not produceundue decomposition by pyrolytio reaction.

The time of blowing may be fairly brief, for

example, 8-10 hours; or it may be quite extensive, for instance, as longas 10-12- -14 days, the longer time periods being employed generallywhen the beginning of the reaction,

above the boiling tem ra e is ust slightly pe W 1 iswithairat alysis ofOils, Fats, and Waxes, by Lewkowitsch,

Sixth'Edition, Volume 2, page 406) produces relatively smallmodifications of certain important indices, such as the iodine value,the acetyl value, and the saponification value. If drastic oxidationtakes place, either by continued mild oxidation, or by more vigorousoxidation from the very as induced by either a higher reactiontemperature a catalyst, then there is obtained an oxidized oil havingcharacteristics which clearly indicate that drastic oxidation has takenplace. These indices of drastic oxidation are a relatively low iodinevalue, such as or less, and may be as low as 40, or thereabouts; 215 to28 3, or thereabouts; an acetyl value of approximately -200; anincreased viscosity such that the material may be hardly mobile atordinary temperatures; a specific gravity of almost one, or a trifleover one at times; an increased refractive index;'and, in the absence ofother coloring matter, a yellow to deep orange. color. The color attimes may since some oxidized castor oils are bleached to make themparticularly adaptable for use as plasticizers in light colored resinoidbodies.

Drastically-oxidized castor oil can be prepared by well known methods,or such products can be purchased in the open market under various tradenames, such as blown castor oil, blended castor oil, blended bodiedcastor oil, "processed castor oil, oxidized castor oil, heavy castoroil," viscous castor oil, etc. These various trade names appear to beapplied to drastically-oxidized castor oils which differ merely indegree but not in kind.

The color of these oils is still pale or light colored in comparisonwith the oil from which they have been derived. Usually they are fairlytransparent, particularly in reasonably thin layers, for instance, aninch or less. Such oils represent greater or lesser degrees of partialoxidation in the'sense that there is a drastic change in comparison withthe change that takes place when a film of castor oil is exposed to air.

For the sake of differentiation, oils of the kind previously describedwill be referred to as pale blown, drastically-oxidized castor oils; andthe or the presence of' v a saponification value of be a questionableindex,

Hydroxyl number Percent unsaponifiable matter 1.1

- volve one or more same terminology is intended to apply to all otherricinoleic bodies of the kind hereinafter described. In addition to-paleblown, drasticallyoxidized castor oil, there is also another type of thekind described in U. S. Patent No. 2,023,979,

' to Stehr, dated December 10, 1935. The product described in said Stehrpatent is characterized by the fact that drastic oxidation is continuedpast the stage where a pale blown oil is obtained and where,.as a matterof fact, a super oxidized productof almost semi-livery consistency isobtained.

Such products are usually much darker in color than the pale blowncastor oils, for the reason that certain side reactions occurwith theformation of dark colored by-products; and as a result, the transparencyor the oil has greatly decreased or disappeared, and it is in nature.

apt to be opaque Attention is directed particularly to U. S. Patent No.2,183,487, dated December '12, 1939, to

aerate pounds of unknown nature or stability, which affect the hydroxylvalue determination. For convenienc in the present instance, one may vconsider blown triricinolein in the same'manner obtaining a technicallypure blown triricinolein and subjecting such material tohydroxyacetylation instead of employing blown castor oil.

Thus, the product particularly contemplated in the present instance isthe compound or compounds obtained by the hydroxyacetylation of Colbeth,to the extent that it discloses detailslas 1 tothe oxidation of castoroil in a manner that is J particularly desirable.

.Our preference is to subject a pale blown castor oil j of the followingcharacteristics, to hydroxyinsu a o "Acid number's 15.1 to 25.0Saponiflcation number 230.5 to 274.0 Iodine number' 43.5 to 55.0

'Acetyl number; 164.0 to 192.0

Percent so;

The production of hydroxyacetylated blown castor oil or similarcompounds is comparatively simple and is comparable to the manufactureof acetylated castor 011, except that hydroxyacetic acid or itsequivalent, such as the anyhydride or acyl chloride, is employed.and'castor oil is replaced by the blown product. In view of the acetylor hydroxyl value of blown castor oil, the principal reaction isobviously an esterification reaction in which the reaction is hastenedor caused to go to completion by removal 01' any water formed. The

usual procedures for promotion of esterification are well known, andinoi the following: Employment of a temperature high enough to eliminateany water formed, for instance, l20 l80 C.; sometimes the presence of astrong acid, such as a benzene-sulfonic acid in small amounts acts as acatalyst; sometimes it is expedient to pass an inert dried gas throughthe reacting mixture: at other times esterification may be conducted inthe presence of a high boilin water-insoluble solvent. such as xylene orthelike, which assists in removing the the condensate so derived, bothfrom the water vapor. and solvent vapor, is separated by gravity; andthe solvent returned to the reacting chamber for further use.

The selection of suitable amounts of reactants in the manufacture oihydroxyacetylated blown castoroil is. of course. simple. The biownoilmay be analyzed so as to determine its hyrcxyl or acetyl value. Suchvalue may be interpreted on the basis of each fatty acid radicalpresent. The acetyl value or hydroxyl value may not correspond exactlyto the alcoholic hydroxyl radicals attached to each high molal fattyacid acyl radical, but such value does correspond. at leastapproximately. The reason is that there may be present anyhydrides, orpossibly, some comwater. in the form of vapors;

blown castor oil. For purposes of convenience,

reference will be made to mono-hydroxyacetylated blown castor oil,di-hydroxyacetylated blown castor oil, and tri-hydroxyacetylated blowncastor oil. Examination of the reaction between hydroxyacetic acid andcastor oil, or

hydroxyacetic acid and blown castor oil, indi-' cates that water isformed and must be removed. Actually, the water formed may notnecessarily be removed instantly, and thus, the water may undergocertain obvious reactions." Likewise, for reasons of economy, it may bedesirable to use a highly concentrated hydroxyacetic acid instead of theanhydrous material as the selected reactant. In such instances, thewater would readily enter into hydrolytic reactions with the blowncastor oil, and thus, the product or composition which' is actuallyhydroxyacetylated, may include compounds comparable to ricinoleic acid,polyricinoleic acid, monoricinolein and diricinolein. Generlcally, theexpression superglycerinated fats," or superglycerinated triricinoleinrefers to the mono-gly'cerides and di-glycerides are present.

. Specific terminology indicated in the present intained byhydroxyacetylation of glycerol, but it is to be noted that suchmaterialmay be prescut cogenerically, for reasons indicated. Earlier referencesto the compounds herein contemplated, and particularly for use as ademulsifier, include hydroxyacetylated derivatives of blown ricinoleicacid compounds, and such expression is now suitably qualified so as tobe limited to blown castor oil, blown triricinolein, blownsuperglycerinated castor oil, and blown castor oil estolides, and otherspecific compounds mentioned subsequently. The preferred example is theco'generic mixture obtained by the hydroxyacetylation oi blown castoroil. One may employ superglycerinated blown castor oil obtained byreaction between blown castor oil and glycerine, in the proportion 01'one or two moles of glycerol per mole of blown castor oil. This simplymeans that the product is obtained by rearrangement instead ofhydrolysis. Obviously, one may also employ technically pure blownmonoriclnolein, technically pure blown diricinolein, and technicallypure blown ricinoleic acid.

mixture in which the- 2,079,762, dated May 11,

- Although a is believed," in viewer what has been. said that no furtherdescription is necessary'in regard to the manufacture-oihydroxyacetylated. blown ricinoleic acid 'compoundsthc. followingexamples are included byway of illus- Y tratien:

HYDROXYACE'IYLATED Br.owN,C1 isroR On.

Example 1 1,000 pounds of pale blown castor oil correspending to thetabular specification :above is treated with 111 pounds ofconcentratedhydroxyacetic acid containing 30 percent of' water. The reaction isconducted at ZOO-250 C. for approximately 2' hours. Completeness inreaction is indicated by the fact that elimination of water practicallyceases, decrease in acid value and hydroxyl value of mixture, andelimination-offree hydrexyacetic acid. The procedure is conducted in theusualreaction vessel of the, kind employed for 'esterificatien, and maybe constructed of any material which is resistant to the reactants. Theamount of hydroxyacetic acid selected'in the present instance iscalculated so as to give substantially a monohydroxyacetylated blowncastor oil.

:HYDROXYACQIYLATED BLowN'CAs'ros On.

Eicample 2 The same procedure is employed as invExa'mple 1, preceding,except that twice the amount of hydroxyacetic acid is used.

Hynaoxrscn'rns'mb BaownCssren On. Example 3 The same procedure isfollowed as in Example 1, preceding except that three times the amountof hydroxyacetic acid is employed so as to yield substantially atri-hydroxyacetylated blown caster oil.

HYDROXYACETYLATED BLOWN CAsroa On.

' Example 4 The same procedure is followed as in Exampics 1 to 3,precedin zexcept that anhydrous hytor oil is contemplated. In view orsuch facts, it becomes even more difllcult to attempt to indieate thenature of the productsebtained' by hydroxyacetylation of blowncastor oilor. the like. As has been previously indicated, esterification, andquite frequently, hydrolysis enters. into the reaction, and it is quiteprobable, especially when aqueous hydroxyacetie acid is employed, thatrearrangement, as exemplified by the formation of estolides,'may takeplace.

- Previous reference has been made to certain specific hydroxyacetylatedderivatives of blown ricinoleic acid compounds. These additionalmembers-include blown diricinolein, blown monericinelein,superglycerinated blown ,castor oil, i. e., castor oil which has beenblown and then 'superglycerinated, as difierentiated from one which issuperglycerinated and then blown, and also blown ricineleic acid andblown polyricinoleic acid. v

The herein described chemical compounds or products are of distinctvalue as a break inducer in the doctor treatment of gasoline or thelike, as

described in U. S. Patent No.'2,.157,223,' to Sut- .ton, dated May 9,1939. Other additional uses include application as plasticizers, inplastics,

synthetic resins, etc., and particularly in the acetate type, i. e., thecellulose acetate, vinyl acetate, and similar types.

Having thus described our. invention, what we claim as new and desire.to secureby Letters Patent is:

1. A hydroxyacetylated drastically oxidized ricineleic acid compoundselected from the class consisting of blown castor oil, blowntriricinolein,

blown 'diricinolein, blown monoricinolein, blown superglyeerinatedcastor oil, superglycerinated droxyacetic acid is employed and water isremoved immediately upon formation. The product so obtained representshydroxyacetylated V blown caster oil, or more especially,hydroxyacetylated blown triricinolein, in the presence of a minimumamount of hydroxyacetylated cogeners.

it is well known that the exact composition or ordinary oxidized casteroil is not known. This has been a matterlei comment from time to time inthe literature, including thepatent literature dealing with the arts inwhich blown casblown caster oil, .blown ricinoleic acid, blownpolyricinolelc acid, and blown castor oil estolides.

2. A hydroxyacetylated drasticallyoxidized caster efl.

3. A tri-hydroxyacetylated drastically-oxidized caster oil.v I l 4. Inthe manufacture of the compound described in claim 1, the steps of: (a)drastic oxidation of a ricinoleic acid compound selected from the classconsisting of blown caster oil, blown triricinolein, blown-diricinolein, blown monericinolein, blownsuperglycerinated castor'.

oil, superglycerinated blown caster oil, blown .ricinoleic acid,- blownpolyricineleic acid and blown castor oil estolides; and (b)hydroxyacetylation of said aforementioned drastically-oxidizedricineleic acid compounds.

MELVIN DE GROOTE. BERNHARD- KEISER. ARTHUR F. wm'rm...

